H atom and heavy atom tunneling processes in tropolone

摘要: The minimum energy pathway leading between the tautomers of tropolone was calculated using molecular orbital (MO) methods. This, with various 1D and 2D cuts potential surface (PES) topography, reveals {tunneling skeleton}/{tunneling H atom} mechanism for tautomerization. In zero-point states atom is localized to one O atoms until skeleton becomes sufficiently vibrationally displaced towards C2v configurations that near-equal double-minimum functions (PEFs) arise vibration. resulting delocalization two sites allows skeletal displacement proceed through barrier tautomerization process be completed. v1 (OH stretching) energies in quantum N1 are strongly dependent on geometry and, adiabatically separated from slow v22 vibration, they contribute markedly different effective V22eff[N1] v22. V22eff[N1=0] a n...